Vat dyestuffs



United States Patent VAT DYESTUFFS Tellis'A.. Martin, Evansville, Ind., and David-I. Randall,

New Vernon, N .J., assignors to General Aniline & Gorporation, New York, N.Y., a corporation of' Delaware No Drawing. Application August 13, 1956 :Serial :No; 6055801 '10 Claims. 01. 260-116) This invention relates to vat dies and relates more particularly to new and valuable vatdyestuffs 'ofqexcellent iastness onmaterials of vegetable fibers, such as cotton, .0

ranging inommed violet 'toolive brown to bluish grey.

An object of this invention is the provisions of new and valuable .vat :dyestuffs'carrying the ldiphenyl sulfone bridge.

Another object of this inventionlis to provide a simple and expeditious process for the preparation of (new and valuable vat dyestuffs by condensing disubstituted, diphenyl sulfones with two vattable residues.

Other objects of this invention will appear from the following-detailed description and claims.

We have'iound that compounds of the general "formula 'ivherein Aryl and Aryl are vattable residues which maybe .thesameor different, are valuable dyestuffs which lye cotton materials in colors of excellent fastness to Twashing, light and chlorine ranging from red-violet to olive-brown to bluish-grey. For example, Any-I and Aryl may be any .of the following vattable residues:

Patented Oct. 13,1959

The newwa't dyestufis of this invention may be pre pared by condensing a di-substituted diphenyl "sulfone with an arylamine as follows:

r Aryl N-E-O-S Or-O-NH Aryl 211. (b) .Em-QSQGNH, 2 am-x where a: may be halogen, chlorine-var bromine;

Of these methods the one found to be most satisfactory involved the reaction bis(4-bromophenyl) sulfone and ArNH This method is considered the more desirable for the synthesis of this series of compound. The reaction is carried out in a suitable solvent, i.e., nitrobenzene, naphthalene, biphenyl, etc. at 180240 C. with an acid acceptor, i.e. sodium carbonate, sodium acetate, etc. and with a catalyst, cupric acetate, cupric chloride, cuprous chloride, etc. in shades which are determined by the nature of the aryl group(s), possess surprisingly good fastness to chlorine, light and washing. It appears that the sulfonyl group -SO has a desirable effect of imparting good fastness properties to this series of dyestuffs.

We also found that carbazolation of these dyestuffs, i.e.

IIIH 0 o IIIH 00 00 II 11TH o o rmooa 00 does not occur easily. However, the reaction can be eflected under fairly drastic conditions in an AlCl -NaCl melt. Here the shades were shifted toward the yellow. The fastness properties of this second class of new dyestufis were also found to be very good.

The instant invention is further illustrated by the following examples which are not intended to be in any way limitative. The parts are by weight.

Example I A mechanically stirred mixture of 18.8 parts of bis(4 bromophenyl) sulfone, 34.2 parts of l-amino-S-benzoylaminoanthraquinone, 14 parts of sodium carbonate, 2 parts of cupric acetate and 482 parts of nitrobenzene was heated at 200-210 C. for four hours. Then a mixture of 6 parts of sodium carbonate and 4 parts of l-amino-S- benzoylaminoanthraquinone was added. The reaction was completed by heating at 200-210 C. for an addi tional hour. When cool, the reaction mixture was diluted with 240 parts of alcohol. The precipitated product was collected on a filter, Washed with alcohol, acetone and water. The wet filter cake was stirred for one hour with dilute hydrochloric acid. The dyestuif t G- 0* t NH (I) (I) NH (50 (50 was collected on a filter, washed and dried. 38 parts (84.5%) of red-brown solid were obtained. From a deep red brown vat cotton is dyed in red brown shades of excellent fastness to chlorine, light and wash.

Carbazolation of 10 parts of this dyestufi resulted by heating at 185-195 C. for ten minutes in a melt of 80 parts of anhydrous aluminum chloride and 20 parts of sodium chloride. At 140-160 C., the reaction mixture Was poured into ice-water containing hydrochloric acid.

The resulting dyestuffs, varying The product was collected on a filter, washed, stirred at -95 C. with 2000 parts of water, and sodium hypochlorite solution was added in portions of 10 parts each until a positive test for chlorine is shown (starch-potassium iodide paper) after one hour from the time of the last addition. The purified product 6 NH (50.. to.

was collected on a filter, washed and dried. 6 parts of of yellow brown solid were obtained. This dyestuif dyes cotton in yellow brown shades of good fastness (light, 104 hours).

Example 11 A mixture of 18.8 parts of bis(4-bromophenyl) sulfone, 36 parts of 1-amino-4-benzoylaminoanthraquinone, 15 parts of sodium carbonate, 2 parts of cupric acetate, and 711 parts of nitrobenzene was heated at 200-210 C. for six hours. On cooling, the precipitated product (i NH NE A A mixture of 9.4 parts of bis(4-bromophenyl) sulfone, 18 parts of 4-aminoanthraquinone-1,2-acridone, 7.5 parts of sodium carbonate, 1.5 parts of cupric acetate and 422 parts of nitrobenzene was heated at 200-210 C. for six hours. On cooling, the precipitated product was collected on a filter, washed with dichlorobenzene, ethanol and acetone. 15 parts of green solid were obtained. It vats to give a dark green vat from which cotton is dyed in olive green shades of fair fastness properties.

, Example IV A mixture of 9.4 parts of bis(4bromophenyl) sulfone,

8.5 parts of 1-amino-S-benzoylaminoanthraquinone, 8.5

parts of 1-amino-4-benzoylaminoanthraquinone, 6 parts of sodium carbonate, 2 parts of sodium acetate, 1 part of eupric acetate .and482 parts ofnitrobenzene was heated in the usual manner for five hours and the product NH r m do. 00 was isolated according to Example 111. 15 parts of blueviolet solid were obtained. 0 Cotton is dyed from a red brown vat of this compound in red-violetshades ofgood fastness properties.

Example V A mixture of 18.8 parts of bis(4-bromophenyl) sulfone, 17 parts of 1-amino-5-benzoylaminoanthraquinone, 17 parts of 4-aminoanthraquinone 1,2-acridone, 15 parts of sodium carbonate, 3 parts of sodium acetate, 2 parts of cupric acetate, and 723 parts of nitrobenzene was treated in the usual manner, and gave 25 parts of product.

W &

Example VI Except for the use of l-amino-4-benzoylaminoanthra- I quinone instead of l-arnino-S-benzoylaminoanthraquinone, the procedure employed here was identical to that employed in Example V. 35 parts of dull blue solid are obtained. The dyestufi II I gives a purplish-brown vat from which cotton is dyed in blue-grey shades.

It is to be understood that the foregoing detailed description is merely given by way of illustration and that many variations may be made therein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by Letters Patent is:

1. The vat dyestufi" of the formula Arylr NHC -s GPO-NH Arylrr wherein Aryl and Aryl are anthraquinone radicals selected from the group consisting of unsubstituted anthraquinonyl, 3-benzamido-anthraquinonyl, 4-benzamido-anthraquinonyl, and 4-anthraquinone-2,1(N)benzacridonyl.

2. The vat dyestufi of the formula.

,3 The vat dyestufi of the formula 4. The vat dyestuif of the formula 6 C O C I l The vat dyestuif of the formula I IIIH 25 NH 6. The vat dyestufi of the formula 00 NH G... t $0 7. The vat dyestutf of the formula AtylrNH-O-SOz-ONHAryln wherein Aryl and Aryl are anthraquinone radicals selected from the group consisting of unsubstituted anthraquinonyl, 3-benzam1ao-anthraquinonyl, 4-benzamido-anthraquinonyl, and 4-anthraquinone-2,l (N)-benzacridonyl which comprises reacting bis(4-bromophenyl) sulfone and at least one aminoanthraquinone, selected from the group consisting of l-aminoanthraquinone, l-amino-S-benzoylaminoanthraquinone, 1-arnino-4-benzoylaminoanthraquinone and 4-arninoanthraquinone-1,2-acridone, in a solvent therefor selected from the group consisting of nitrobenzene, naphthalene, biphenyl and quinoline at a temperature of 180 to 240 C. in the presence of an acid acceptor, selected from the group consisting of sodium carbonate and sodium acetate, and a catalyst selected from the group consisting of cupric acetate and cuprous chloride.

8 References Cited in the file of this patent UNITED STATES PATENTS 1,037,410 Bally Sept. 3, 1912 2,353,041 Klein July 4, 1944 2,628,230 Stilmar Feb.' 10, 1953 FOREIGN PATENTS 14,225 Great Britain Mar. 14, 1912 Of 1911 Reinhold Pub. Corp., New York 1955), pp. 440-441. 

1. THE VAT DYESTUFF OF TH FORMULA
 4. THE VAT DYESTUFF OF THE FORMULA 